氧化石墨烯纳米带杂化粒子和石墨烯纳米带的研究进展

氧化石墨烯纳米带杂化粒子是将氧化石墨烯纳米带(GONRs)与其他纳米粒子经π-π键、氢键等结合方式复合在一起,通过这种特殊的结合形态一方面可以有效地防止GONRs的聚积,另一方面新的纳米粒子的引入能够赋予该杂化材料某些特殊的性能,从而有利于充分发挥GONRs杂化材料在聚合物改性等领域的综合性能。本文综述了氧化石墨烯纳米带杂化粒子的制备方法、性能和应用现状。此外,针对GONRs的还原产物石墨烯纳米带(GNRs)的结构、性能、制备方法及其应用领域也进行了系统性地论述。相关研究表明,氧化石墨烯纳米带杂化粒子的设计与制备是氧化石墨烯纳米带迈向实用领域的一个有效途径,而石墨烯纳米作为石墨烯的一种特殊结构的二维变体,继承了石墨烯优良的导电和导热等性能,同时特殊的边缘效应,因而呈现出了更广阔的应用潜力。     

石墨烯及Ag/石墨烯纳米复合材料的原位合成

选择改进的H ummer方法制备氧化石墨烯;采用硼氢化钠和柠檬酸钠相结合的方法还原氧化石墨制备石墨烯及Ag/石墨烯纳米复合材料,采用拉曼光谱、TEM、SEM、UV-Vis、XRD、FTIR等多种测试手段对其表征,发现硼氢化钠可以还原氧化石墨烯中的边缘缺陷,柠檬酸钠可以剥离氧化石墨烯片层并使银纳米颗粒附着在石墨烯片层上,石墨烯层数较少且随着反应时间的延长,银纳米颗粒的尺寸也会逐渐增大.     

石墨烯分散液的制备以及应用前景

石墨烯因独特的晶体结构和丰富新奇的光电性能而成为研究前沿和热点。高浓度稳定分散的石墨烯分散液有着巨大的应用前景,可广泛应用于能源存储、电子信息、功能材料等多个领域。但石墨烯纳米片不亲水也不亲油,易发生团聚,难以长时间稳定分散在溶液中。本文分析了石墨烯在不同溶剂中的溶解性,综述了当前国内外一些石墨烯分散液的制备方法和开发前景,指出分子修饰法将是石墨烯分散液功能化制备的发展方向,这为石墨烯分散液的功能化应用提供了重要的参考。     

石墨烯/氧化石墨烯-聚乳酸的制备与表征

通过优化Hummers法制备了氧化石墨烯,并用水合肼还原法制备了石墨烯,且对自制的石墨烯和氧化石墨烯进行了测试及分析;然后通过溶液插层法制得纳米级聚乳酸/石墨烯和聚乳酸/氧化石墨烯复合材料,并对其分散性、热学性能以及力学性能进行了分析。对石墨烯和氧化石墨烯的表征结果说明,水合肼可以还原氧化石墨,所制备的石墨烯纯度较高。对聚乳酸/石墨烯和聚乳酸/氧化石墨烯复合材料的性能分析结果表明,在聚乳酸的结晶度、结晶速率和对聚乳酸的结晶成核上,石墨烯比氧化石墨烯具有更优异的表现,但在热稳定性能方面,氧化石墨烯比石墨烯优异;在力学性能方面,有增强和降低两种影响,添加少量氧化石墨烯时聚乳酸的力学性能降低,而含质量分数为0.5%的石墨烯复合材料在拉伸实验和冲击实验中的增强效果较为明显。     

From Graphite to Graphene Oxide and Graphene Oxide Quantum Dots

Many methods have been reported for synthesizing graphene oxide (GO) and graphene oxide quantum dots (GOQDs) where a tedious operational procedure and long reaction time are generally required. Herein, a facile one‐pot solvothermal method that allows selective synthesis of pure GO and pure GOQDs, respectively is demonstrated. What is more, the final product of either GO or differently sized GOQDs can be easily controlled by adjusting the reaction temperatures or reactant ratios, which is also feasible when enlarged to gram scale. The 2.5 nm GOQDs show excellent photoluminescence that can be utilized for bioimaging or distinctive detection of Eu³⁺ and Tb³⁺ from their respective mixtures with other rare earth and/or transition metal ions, at sub‐ppm level.     

Principles Governing Control of Aggregation and Dispersion of Graphene and Graphene Oxide in Polymer Melts

Controlling the structure of graphene and graphene oxide (GO) phases is vitally important for any of its widespread intended applications: highly ordered arrangements of nanoparticles are needed for thin-film or membrane applications of GO, dispersed nanoparticles for composite materials, and 3D porous arrangements for hydrogels. By combining coarse-grained molecular dynamics and newly developed accurate models of GO, the driving forces that lead to the various morphologies are resolved. Two hydrophilic polymers, poly(ethylene glycol) (PEG) and poly(vinyl alcohol) (PVA), are used to illustrate the thermodynamically stable morphologies of GO and relevant dispersion mechanisms. GO self-assembly can be controlled by changing the degree of oxidation, varying from fully aggregated over graphitic domains to intercalated assemblies with polymer bilayers between sheets. The long-term stability of a dispersion is extremely important for many commercial applications of GO composites. For any degree of oxidation, GO does not disperse in PVA as a thermodynamic equilibrium product, whereas in PEG dispersions are only thermodynamically stable for highly oxidized GO. These findings—validated against the extensive literature on GO systems in organic solvents—furnish quantitative explanations for the empirically unpredictable aggregation characteristics of GO and provide computational methods to design directed synthesis routes for diverse self-assemblies and applications.     

石墨烯的制备研究进展

近年来, 石墨烯以其独特的结构和优异的性能, 在化学、物理和材料学界引起了广泛的研究兴趣. 人们已经在石墨烯的制备方面取得了积极的进展, 为石墨烯的基础研究和应用开发提供了原料保障. 本文大量引用近三年最新参考文献, 综述了石墨烯的制备方法: 物理方法(微机械剥离法、液相或气相直接剥离法)与化学法(化学气相沉积法、晶体外延生长法、氧化?还原法), 并详细介绍了石墨烯的各种修饰方法. 分析比较了各种方法的优缺点, 指出了石墨烯制备方法的发展趋势.     

Graphene Oxide,Highly Reduced Graphene Oxide,and Graphene: Versatile Building Blocks for Carbon‐Based Materials

Isolated graphene, a nanometer‐thick two‐dimensional analog of fullerenes and carbon nanotubes, has recently sparked great excitement in the scientific community given its excellent mechanical and electronic properties. Particularly attractive is the availability of bulk quantities of graphene as both colloidal dispersions and powders, which enables the facile fabrication of many carbon‐based materials. The fact that such large amounts of graphene are most easily produced via the reduction of graphene oxide—oxygenated graphene sheets covered with epoxy, hydroxyl, and carboxyl groups—offers tremendous opportunities for access to functionalized graphene‐based materials. Both graphene oxide and graphene can be processed into a wide variety of novel materials with distinctly different morphological features, where the carbonaceous nanosheets can serve as either the sole component, as in papers and thin films, or as fillers in polymer and/or inorganic nanocomposites. This Review summarizes techniques for preparing such advanced materials via stable graphene oxide, highly reduced graphene oxide, and graphene dispersions in aqueous and organic media. The excellent mechanical and electronic properties of the resulting materials are highlighted with a forward outlook on their applications.     

石墨烯湿敏性能研究进展

湿度传感器与大气监测、工业生产和生物医疗等领域息息相关。随着科技的不断发展,人们对高性能湿度传感器的需求不断增加,这为湿度传感器行业的发展带来了前所未有的机遇和挑战,其中高性能湿敏材料的开发尤为关键。在诸多湿度传感器中,金属氧化物或金属氧化物/聚合物复合材料湿度传感器因其敏感元件选择的多样性、易于后加工处理和响应特性高等特点而受到广泛关注。与聚合物湿度传感器相比,陶瓷材料的合成过程更简便,响应也通常更为迅速,且聚合物的成本更低。近些年,新型纳米材料被广泛应用于湿度传感器领域,逐渐成为湿敏材料的主要发展方向及研究热点。零维和一维纳米碳质材料,如富勒烯、碳纳米管作为湿敏活性层制备的传感器通常具有大比表面积、可室温下工作、易于实现微型化、稳定性好等诸多优点,但它们的零维或一维结构与现有的平面电子器件加工工艺不相匹配。石墨烯是由sp2杂化的碳原子紧密排列构成的二维蜂巢晶格结构的单层石墨,其独特的二维结构适用于现有的平面电子器件加工工艺。石墨烯材料作为湿敏活性层受到研究者们的广泛关注是因为它具备诸多优异特性:(1)石墨烯的所有原子都在表面,具有超大的比表面积,原则上,石墨烯传感器的动态检测范围可以从单个分子到很高的浓度水平;(2)利用石墨烯的电学特性和力学特性可以很好地进行传感信号的转换;(3)金属、聚合物或其他修饰剂功能化的石墨烯能与特定分子发生相互作用,大大增强传感器的选择性;(4)石墨烯单晶可以制作四探针装置,从而能够避免接触电阻的影响,并大大提高灵敏度;(5)与其他纳米碳材料如碳纳米管相比,石墨烯和氧化石墨烯制备成本更低。本文综述了石墨烯湿敏性能及其应用的研究进展,着重讨论了本征石墨烯、氧化石墨烯和改性石墨烯的湿敏特性。文章最后分析了石墨烯基湿度传感器未来的发展方向和面临的挑战。     

Graphene oxide (GO)-based wideband optical polarizer using a non-adiabatic microfiber

In this paper, a microfibre polarizer based on graphene oxide (GO) is proposed and demonstrated. A microfibre was coated with GO using the drop-casting technique. The extinction ratio (ER) has been measured at wideband range of 1310, 1460, 1550 and 1600 nm. The highest ER obtained in this experiment was 37.0 dB measured at 1480 nm wavelength. The result has been achieved with a GO coating thickness of 24 μm and coating length of 12 mm. This work demonstrates a polarizing effect of GO-coated microfibre.     

Tailored Crumpling and Unfolding of Spray‐Dried Pristine Graphene and Graphene Oxide Sheets

For the first time, pristine graphene can be controllably crumpled and unfolded. The mechanism for graphene is radically different than that observed for graphene oxide; a multifaced crumpled, dimpled particle morphology is seen for pristine graphene in contrast to the wrinkled, compressed surface of graphene oxide particles, showing that surface chemistry dictates nanosheet interactions during the crumpling process. The process demonstrated here utilizes a spray‐drying technique to produce droplets of aqueous graphene dispersions and induce crumpling through rapid droplet evaporation. For the first time, the gradual dimensional transition of 2D graphene nanosheets to a 3D crumpled morphology in droplets is directly observed; this is imaged by a novel sample collection device inside the spray dryer itself. The degree of folding can be tailored by altering the capillary forces on the dispersed sheets during evaporation. It is also shown that the morphology of redispersed crumpled graphene powder can be controlled by solvent selection. This process is scalable, with the ability to rapidly process graphene dispersions into powders suitable for a variety of engineering applications.     

Nafion改性多级孔径石墨烯气凝胶制备与性能研究

通过溶胶-凝胶法制备了孔径小于1 μm的多级孔径新型石墨烯气凝胶。制备过程中, 首先通过Nafion对氧化石墨烯(GO)表面进行化学修饰, 并利用乙二胺还原制备石墨烯水凝胶, 最终通过冷冻干燥形成石墨烯气凝胶。实验发现Nafion可以有效减少制备过程中氧化石墨烯的团聚, 使石墨烯气凝胶形成多级孔径形貌。所得石墨烯气凝胶的孔径可控制在1 μm以内, 远小于传统石墨烯气凝胶材料的孔径(20~100 μm)。这种具有独特结构的石墨烯气凝胶表现出优异的性能, 例如高比表面积, 高孔隙率, 其电化学电容性能相对传统气凝胶提高了约40%。     

Biotransformation and Biological Interaction of Graphene and Graphene Oxide during Simulated Oral Ingestion

The biotransformation and biological impact of few layer graphene (FLG) and graphene oxide (GO) are studied, following ingestion as exposure route. An in vitro digestion assay based on a standardized operating procedure (SOP) is exploited. The assay simulates the human ingestion of nanomaterials during their dynamic passage through the different environments of the gastrointestinal tract (salivary, gastric, intestinal). Physical–chemical changes of FLG and GO during digestion are assessed by Raman spectroscopy. Moreover, the effect of chronic exposure to digested nanomaterials on integrity and functionality of an in vitro model of intestinal barrier is also determined according to a second SOP. These results show a modulation of the aggregation state of FLG and GO nanoflakes after experiencing the complex environments of the different digestive compartments. In particular, chemical doping effects are observed due to FLG and GO interaction with digestive juice components. No structural changes/degradation of the nanomaterials are detected, suggesting that they are biopersistent when administered by oral route. Chronic exposure to digested graphene does not affect intestinal barrier integrity and is not associated with inflammation and cytotoxicity, though possible long‐term adverse effects cannot be ruled out.     

Controllable Synthesis of Doped Graphene and Its Applications

Graphene is a wonder material with the ultimate smallest thickness that is readily accessible to various approaches for engineering its excellent properties. Graphene doping is an efficient way to tailor its electric properties and expand its applications. This topic covers wide research fields and has been developing rapidly. This article presents a broad and comprehensive overview of the developments in the preparation and applications of doped graphene including doping methods, doping levels, doping effect and types of heteroatoms. Very recent advances are also presented. In addition, existing problems in terms of achieving greater control over and further developments of doped graphene are also discussed.